Catalyst and process for the production of aldehydes by hydroformylation of olefinically unsaturated compounds

ABSTRACT

A catalyst comprising rhodium and a compound of the formula (I)                    
     in which 
     m is a number from 1 to 1000; 
     x is a number from 0 to 4; 
     W is a group of the formulae —CH 2 —CH 2 —, —CH(CH 3 )CH 2 —or —CH 2 CH(CH 3 )—; 
     R is hydrogen, a straight-chain or branched C 1 -C 5 — alkyl radical; or a group of the formulae                    
     where 
     a, b, c, d and e independently of one another are a number from 0 to 1000, at least one of the numbers a, b, c, d and e being greater than 0; 
     R 5 , R 6 , R 7 , R 8  and R 9  are identical or different and are hydrogen, C 1 -C 5 -alkyl or a group of the formula                    
     R 1  and R 2  are identical or different and are a straight-chain, branched or cyclic C 1 -C 30 -alkyl radical or C 6 - 10 -aryl radical, which is unsubstituted or substituted by from one to five C 1 -C 3 -alkyl radicals, and 
     L is C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy, NO 2 , NR 3 R 4 , where R 3  and R 4  independently of one another are hydrogen or C 1 -C 4 -alkyl, or L is Cl or OH, 
     for hydroformylation reactions.

This is the U.S. National Stage Application of PCT/EP97/03926 filed Jul.21, 1997.

The invention relates to a novel catalyst and to a process for thehydroformylation of olefinically unsaturated compounds, whosehydroformylation products are insoluble or virtually insoluble in water,in the presence of this catalyst.

It is known that by reacting olefins with carbon monoxide and hydrogen(hydroformylation), it is possible to prepare aldehydes and alcoholswhich contain one more carbon atom than the starting olefin. Thereaction is catalyzed by hydridometal carbonyls, preferably those of themetals of group VIII of the Periodic Table. Besides cobalt, the classiccatalyst metal, catalysts based on rhodium have been increasingly usedfor some years. In contrast to cobalt, rhodium allows the reaction to becarried out at low pressure, and moreover when terminal olefins areused, straight-chain n-aldehydes are formed preferentially andisoaldehydes are formed only to a subordinate degree. Finally, thehydrogenation of olefinic compounds to give saturated hydrocarbons inthe presence of rhodium catalysts is also significantly lower than whencobalt catalysts are used.

In industry, the hydroformylation of olefinically unsaturated compoundsusing the catalytic effect of rhodium-phosphine complex compounds isessentially carried out in two variants. The first involves the processbeing carried out in homogeneous phase, i.e. starting olefin, catalystsystem (rhodium carbonyl and organic phosphine) and reaction productsare present in solution together. The reaction products are separatedoff from the mixture by distillation. The other variant is characterizedby the presence of an aqueous catalyst phase, separate from the reactionproduct, which comprises rhodium carbonyl complexes and a sulfonated orcarboxylated organic phosphine. This variant permits isolation of thehydroformylation products without use of thermal process steps,simplifies catalyst recovery and produces a particularly high proportionof unbranched aldehydes when terminal olefins are used.

Both of these processes are frequently described in the literature, forexample in W. A. Herrmann, C. W. Kohlpaintner, Angew. Chem. 1993,105, p.1588 and also in DE-C-26 27 354 and EP-B-0 103 810.

In the processes which have been implemented in industry, the rhodiumcatalyst is used in the form of hydridorhodium carbonyls which containadditional ligands, in particular tertiary organic phosphines orphosphites. In most cases, the ligands are present in excess relative tothe metal atom, so that the catalyst system consists of complexcompounds and a free ligand. Use of the rhodium catalysts describedmakes it possible to carry out the hydroformylation reaction atpressures below 300 bar.

The different way in which the reaction is carried out affects interalia the extent of conversion of starting materials and the formation ofby-products. In general, the process in the two-phase reaction mediumgives better conversions at higher selectivity than the homogeneous(single-phase) process. An advantage of the reaction in the system withseparate catalyst phase is the trouble-free removal of the catalyst. Itcan be removed by simple separation of aqueous and organic phases, i.e.without distillation and thus without thermal process steps. On theother hand, in single-phase homogeneous catalyzed processes, thereaction product has to be distilled off from the catalyst, or thecatalyst has to be separated off from the crude product by anothermethod. Due to the thermal sensitivity of the reaction products,distillation is frequently associated with losses in yield. Otherprocess variants, such as, for example, precipitation or membraneseparation of the catalyst are industrially complex and thusdisadvantageous.

The two-phase hydroformylation process has proven successful for thehydroformylation of propene and 1-butene (from butene mixtures, e.g.raffinate 2) on an industrial production scale. It is known as theRuhrchemie/Rhône-Poulenc process. The catalyst system used is ahydridorhodium carbonyl complex which is modified and stabilized by thewater-soluble ligands TPPTS (triphenylphosphine trisulfonate sodiumsalt).

The TPPTS ligand, which is water-soluble by virtue of the sulfonatogroups, has the function of solubilizing the rhodium complex in thewater phase and of preventing loss of the rhodium complex into theorganic phase. The chemical reaction, i.e. the complex-catalyzedaddition of a hydrogen and a carbon monoxide molecule to the double bondtakes place, according to current understanding, either in the aqueouscatalyst phase or in the phase interface. The product formed can passinto the organic phase by adjusting the phase equilibrium.

For the hydroformylation of higher olefins, i.e. olefins having morethan 6 carbon atoms, the Ruhrchemie/Rhône-Poulenc process is unsuitablesince only very low space-time yields are obtained. The decrease in therate of the reaction during the two-phase hydroformylation of olefins,which is observed with increasing carbon number, is generally attributedto the poorer solubility of the higher olefins in the water phase. Sincethe two-phase hydroformylation process has both the advantage ofrelatively mild reaction conditions, as well as permitting simpleseparation of the product phase from the catalyst phase, there is anindustrial interest in also hydroformylating higher olefins by thisprocess.

The hydroformylation products of higher olefins are mostly used asintermediates for the preparation of higher alcohols and, to a lesserextent, for the preparation of medium- to long-chain carboxylic acids byoxidation, or for the synthesis of amines by reductive amination ofaldehydes. Moreover, straight-chain aldehydes having seven or morecarbon atoms are used in the fragrance industry as such or in the formof their acetals for perfumes or for perfuming soaps. Linear andbranched alcohols having from 8 to 12 carbon atoms are used industriallyon a large scale as plasticizer alcohols, which are in most cases usedin the form of their bisphthalates or bismaleates as plasticizers forplasticized PVC. Other fields of application for higher, largely linearalcohols are components for detergents, coating base materials andenameling base materials (Ullmann's Encyclopedia of IndustrialChemistry, 4th edition, Vol. 7, publisher Chemie Weinheim 1974, p.118-141). Catalysts for the hydroformylation are also known from J.prakt. Chem. 338 (1996), 124-128.

The object was to develop a process which permits higher molecularweight olefinically unsaturated compounds to be hydroformylated with thehighest possible activity and selectivity to give the correspondingaldehydes. Moreover, it should be possible to readily separate reactionproduct and catalyst system from one another, and noble metal lossesshould be largely avoided.

This object is achieved by a catalyst comprising rhodium and a compoundof the formula (I)

in which

m is a number from 1 to 1000, preferably from 2 to 300, particularlypreferably from 2 to 100;

x is a number from 0 to 4, preferably 0 or 1;

W is a group of the formulae —CH₂—CH₂—, —CH(CH₃)CH₂— or —CH₂CH(CH₃)—;

R is hydrogen, a straight-chain or branched C₁-C₅-alkyl radical; or agroup of the formulae

where

a, b, c, d and e independently of one another are a number from 0 to1000, at least one of the numbers a, b, c, d and e being greater than 0;

R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are hydrogen,C₁-C₅-alkyl or a group of the formula

R¹ and R² are identical or different and are a straight-chain, branchedor cyclic C₁-C₃₀-alkyl radical or C₆-C₁₀-aryl radical, which isunsubstituted or substituted by from one to five C₁-C₃-alkyl radicals,or R¹ and R² together with the trivalent P atom form a dibenzophospholylof the formula

or a 3,4-dimethyiphospholyl of the formula

and

L is C₁-C₅-alkyl, C₁-C5-alkoxy, NO₂, NR³R⁴, where R³ and R⁴independently of one another are hydrogen or C₁-C₄-alkyl, or L is Cl orOH.

The alkylene glycol groups on the phenyl ring can be in the ortho, metaor para position relative to the phosphorus atom. The oxalkylene chainon which the group —(W—O—)_(m) is based can consist exclusively ofethylene oxide units or exclusively of propylene oxide units or of acombination of these units in any order.

Of particular interest are compounds of the formula (I) in which R¹ andR² are identical and are each a straight-chain or branched C₁-C₆-alkylradical, a cyclohexyl radical or a phenyl radical.

Also of particular interest are compounds of the formula (I) in which Ris hydrogen, methyl, ethyl, n-propyl, n-butyl or a group of the formula

in which c¹, d¹ and e¹ independently of one another are a number from 1to 500, in particular from 2 to 300, and R⁷⁰, R⁸⁰ and R⁹⁰ are identicalor different and are hydrogen, methyl, ethyl, n-propyl or n-butyl.

Also of particular interest are compounds of the formula (I) in which Lis methoxy, ethoxy, methyl, ethyl or OH, or in which x is 0.

Examples of compounds of the formula (I) are methyltriphenylphosphin-4-yl triethylene glycol ether, methyltriphenylphosphin-3-yl triethylene glycol ether, methyltriphenylphosphin-2-yl triethylene glycol ether, and compounds havinglonger oxalkyl chains, the ethoxy and propoxy units being in any orderand as a rule forming a product mixture:

in which m₁ and m₂ are each 16 and Ph is phenyl;

in which m₃ is about 22;

in which m₄ is about 84 and m₅ is about 21,

in which m₆ is about 22 and m₇ is 5.5.

Compounds of the formula (I) can be prepared by deprotonating ahydroxyphenylphosphine of the formula (II)

using a base to give the corresponding phenoxide, and reacting with acompound of the formula (III)

X—(—W—O—)_(m)—R  (III)

in which W, R and m are as defined above, and X is a nucleophilicallysubstitutable leaving group, to give the compound of the formula (I).

Examples of nucleophilically substitutable leaving group X are ortho-meta- or para-toluenesulfonate, methanesulfonate, trifluoro acetate,trifluoromethanesulfonate, nonafluorobutylsulfonate, benzenesulfonate,p-nitrobenzenesulfonate, Cl or Br.

Suitable bases are, for example, NaOH, KOH, NaH, KH or trialkylamine.Preference is given to triethylamine and KOH.

The reaction is expediently carried out at temperatures between 20 and100° C., preferably between 60 and 90° C. Since the deprotonation stageis generally exothermic, at this point in the synthesis, cooling may beexpedient, for example to from 0 to 20° C. The process can be carriedout in the presence or absence of organic solvents. Suitable organicsolvents are, in particular, dimethyl formamide, toluene or ethylacetate. It is further advantageous to carry out the reaction under aninert-gas atmosphere.

The catalyst can be prepared in a simple manner by bringing togetherrhodium, for example in the form of a salt or a complex, and thecompound of the formula (I). Examples of such salts or complexes arerhodium acetate, rhodium butyrate, rhodium chloride, rhodiumacetylacetonate, rhodium nitrate, [RhCl(CO)₂], [Rh(acac)(CO)₂] andHRh(CO)(TPP)₃, where acac is acetylacetonate and TPP istriphenylphosphine. It is particularly favorable to dissolve the rhodiumin the form of a water-soluble salt or complex together with a compoundof the formula (I) in water. It is also possible to firstly dissolve therhodium salt or the rhodium complex and then add the compound of theformula (I) or, in reverse, firstly dissolve the compound of the formula(I) and then add the rhodium salt or the rhodium complex.

It is possible to use the catalyst comprising rhodium and the compoundof the formula (I) directly in the hydroformylation, i.e. withoutadditional treatment.

It is, however, also possible to firstly subject the catalyst comprisingrhodium and the compound of the formula (I) to a pretreatment in thepresence of hydrogen and carbon monoxide under pressure and, ifnecessary, at elevated temperature and, by means of thispreconditioning, to prepare the actually active catalyst species. Theconditions for the preconditioning can correspond to the conditions of ahydroformylation.

The catalyst usually comprises rhodium and the compound of the formula(I) in a molar ratio of from 1:1 to 1:5000, in particular from 1:100 to1:3000. In a number of cases, a catalyst comprising rhodium and thecompound of the formula (I) in a molar ratio of from 1:1 to 1:1500, inparticular from 1:1 to 1:200, preferably from 1:50 to 1:150 has alsoproven suitable. In general, increasing amounts of phosphine ligandseffect a reduction in the loss of noble metal into the organic phaseduring the hydroformylation.

The present invention further provides a process for the preparation ofaldehydes. It comprises reacting an olefinic compound having from 3 to20 carbon atoms with carbon monoxide and hydrogen in the presence of acatalyst comprising rhodium and a compound of the general formula (I) ata pressure of from 10 to 500 bar and a temperature of from 40 to 200° C.in a reaction mixture which comprises an aqueous and an organic phase.

The liquid organic phase essentially consists of the substrate olefinand/or the reaction product of the hydroformylation and, wherenecessary, one or more organic solvents. If a solvent is used, it may bechosen from inert aliphatic compounds, such as alkanes, preferablyC₅-C₉-alkanes, such as cyclohexane and n-pentane, or aromatic compounds,such as toluene, xylene, ethylbenzene, mesitylene or chlorobenzene.

The aqueous phase comprises the catalyst and the compound of the formula(I). It is advantageous to form the catalyst in situ from theabovedescribed rhodium salt or rhodium complex and the compound of theformula (I) in the aqueous phase during the hydroformylation accordingto the invention. As mentioned above, it is advantageous if the catalystcomprises a stoichiometric excess of the phosphine of the formula (I).

A stoichiometric excess of the phosphine is thus advantageously added tothe reaction mixture in order to form the catalytic complex and toprovide free phosphine. The free phosphines can be identical ordifferent to those used for the formation of the catalytic complex,although it is preferable to use the same ones.

The volume ratio of organic phase to aqueous catalyst phase should bebetween 5:1 and 1:5. Preference is given to a range from 3:1 to 1:2. Lowquotients of aqueous to organic phase in most cases effect a slowing ofthe reaction rate. In the case of high volume ratios of aqueous toorganic phase, the loss of rhodium into the organic phase is higher.

The olefinic compound may comprise one or more as a carbon-carbon doublebond. The carbon-carbon double bond can be positioned at the end orinternally. Preference is given to olefinic compounds with a terminalcarbon-carbon double bond.

Examples of α-olefinic compounds (having a terminal carbon-carbon doublebond) are alkenes, alkyl alkenoates, alkylene alkanoates, alkenyl alkylethers and alkenols, in particular those having from 6 to 14 carbonatoms. Without laying claim to completeness, α-olefinic compounds whichmay be mentioned are propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-decene, 1-dodecene, 1-octadecene,2-ethyl-1-hexene, styrene, 3-phenyl-1-propene, allyl chloride,1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, hex-1-en-4-ol,oct-1-en-4-ol, vinylcyclohexene, n-propyl-7-octenoate, 7-octenoic acidand 5-hexenamide.

Examples of other suitable olefinic compounds which may be mentioned are2-butene, diisobutylene, tripropylene, ®Octol or ®Dimersol (dimerizationproducts of butenes), tetrapropylene, cyclohexene, cyclopentene,dicyclopentadiene, acyclic, cyclic or bicyclic terpenes, such asmyrcene, limonene and pinene.

The abovedescribed catalyst comprising rhodium and the compound of theformula (I) is usually used in an amount of from 5 to 100 mg, preferablyfrom 30 to 60 mg, of rhodium per kilogram of aqueous phase.

The amount of rhodium relative to the olefinic compound is expedientlyfrom 1:500 to 1:100,000, preferably from 1:10,000 to 1:80,000, mol ofrhodium per mole of olefinic compound. The fact that such small amountsof rhodium suffice for a two-phase process is extremely surprising.

In the process according to the invention rhodium loss into the organicphase is in most cases below 1 ppm.

The pH of the aqueous phase should preferably be at pH 5 to 8. If abuffer is used, it should be compatible with the catalyst and be inert.

The reaction is carried out in the presence of hydrogen and carbonmonoxide (synthesis gas). The molar ratio of hydrogen to carbon monoxidecan be chosen within wide limits and is usually from 1:10 to 10:1, inparticular from 5:1 to 1:5, preferably from 2:1 to 1:2. The process isparticularly simple if hydrogen and carbon monoxide are used in a molarratio of 1:1 or approximately 1:1.

In a large number of cases, it has proven advantageous to carry out thereaction at a pressure of from 20 to 400 bar, in particular from 30 to80 bar. While 80 bar is preferable from the point of view of activity, asynthesis gas pressure of 30 bar gives better selectivities with respectto the n/iso ratio.

The reaction of the olefinic compounds with hydrogen and carbon monoxidetakes place at temperatures of from 40 to 200° C. Below 40° C. thereaction rate is unacceptably slow, whereas catalyst deactivation cantake place at temperatures above 200° C. A preferred range is from 80 to150° C., particularly preferably from 110 to 130° C., since thesetemperatures give the best results with respect to selectivity toaldehydes, combined with an acceptable reaction rate.

At this point, it should be pointed out that the reaction conditions, inparticular rhodium concentration, pressure and temperature also dependon the nature of the olefinic compound to be hydroformylated. Relativelyreactive olefinic compounds require low rhodium concentrations, lowpressures and low temperatures. In contrast, the reaction of relativelyunreactive olefinic compounds requires greater rhodium concentrations,higher pressures and higher temperatures.

The process can be carried out particularly successfully if anα-olefinic compound is used. It is, however, also possible to reactother olefinic compounds having internal carbon-carbon double bonds.

After a discontinuous reaction is complete, the hydroformylation mixtureis freed from carbon monoxide and hydrogen by depressurization, and theorganic product phase is separated from the aqueous catalyst phase byphase separation. The process according to the invention can, however,also be carried out continuously.

EXPERIMENTAL SECTION

Preparation of a Compound of the Formula (I)

The preparation of compounds of the formula (I) is described in theGerman Patent Application (file reference 196 30534.9) filed on the samedate as the present patent application.

Preparation of the Catalyst

1) 0.7 mg of rhodium(III) acetate and 36 g of the ligandP-(P41/300)-triphenylphosphine prepared in accordance with Example 4 ofthe abovementioned German Patent Application (file reference P 19630534.9) are dissolved in 30 ml of water corresponding to a Rh:ligandmolar ratio of 1:2500, and maintained at 125° C. for 3 h in a 200 mlsteel autoclave at a synthesis pressure of 25 bar (CO/H₂=1:1).

EXAMPLE 1 Hydroformylation of 1-hexene

30 ml of 1-hexene were metered into the abovementioned steel autoclavecontaining the catalyst using a pump under the existing pressure of 25bar, and the mixture is stirred for 3 hours at 125° C. The synthesis gaspressure was increased to 80 bar and kept constant within a pressureband of 5 bar. At the end of the reaction, the stirrer and heating wereswitched off, and after a settling period of from 30 to 60 min, theupper product phase was separated from the catalyst phase by phaseseparation. The degree of conversion of the product phase was analyzedusing gas chromatography (GC) and ¹H-NMR spectroscopy:

Conversion (according to GC) in an experimental series of 5 cyclesrunning one after the other with the same catalyst phase: 97.9%; 98.4%,98.1%, 97.2%, 90.4%. Ratio of n-heptanal:isoheptanal (according to GC):71:29.

EXAMPLES 2 TO 5

The procedure was as given in Example 1, but the olefinic compound (ineach case 120 mmol) and the synthesis gas pressure were changed as givenin the table below:

Conversion Amount of Synthesis gas in % Ratio of Olefin olefin in mlpressure in bar (GC) n:iso (GC) 1-Octene 18.9 30 83.4 77:23 1-Dodecene26.8 30 35.1 77:23 1-Hexene 15.9 80 92.8 72:28 1-Octene 18.9 80 97.573:27

EXAMPLE 6 Experimental Series with 1-octene (7 cycles)

The procedure was as given in Example 1, but using 37.7 ml of 1-octeneas olefin. The following conversions and n:isononanal ratios wereobtained in the individual reaction cycles:

Conversion in % Ratio of Cycle (GC) n:iso (GC) 1 97.1 71:29 2 97.4 71:293 97.5 71:29 4 97.5 70:30 5 97.2 71:29 6 95.4 70:30 7 97.0 69:31

EXAMPLE 7 Experimental Series with 1-dodecene (5 cycles)

The procedure was as given in Example 1, but using 53.3 ml of 1-dodeceneas olefin. The following conversions and n:iso ratios were obtained inthe individual reaction cycles:

Conversion in % Ratio of Cycle (GC) n:iso (GC) 1 79.3 72:28 2 82.0 72:283 83.4 72:28 4 82.2 71:29 5 78.1 70:30

Preparation of the Catalysts used in Examples 8 to 21

General Preparation Procedure:

6 mg of rhodium(III) acetate and the amount, specified in Table I under“initial weight of ligand [g]”, of the ligands prepared in accordancewith the abovementioned German Patent Application (file reference 19 630534.9) are dissolved in 30 ml of water corresponding to an Rh:ligandmolar ratio of 1:100, and maintained at 125° C. for 3 hours in a 200 mlsteel autoclave at a synthesis gas pressure (CO/H₂) of 25 bar withstirring (preconditioning). This catalyst solution is used in Examples 8to 21.

As regards the compounds of the formula (I) used(4′-(diphenylphosphinyl)-phenoxy-polyalkylene glycols), reference may bemade to the following summary.

1 M 350-TPP: m = 5-9 1 (molecular weight about 610) 1 M 500-TPP: m =9-13 1 (molecular weight about 760) 1 M 750-TPP: m = 12-20 1 (molecularweight about 1 1010)

1 PEG 200-TPP: m = 5-7 1 (molecular weight about 560) 1 PEG 600-TPP: m =11-15 1 (molecular weight about 860) 1 PEG 1000-TPP: m = 19-27 1(molecular weight about 1260) 1 PEG 1000-TPP: m = 29-39 1 (molecularweight about 1760)

1 M41/47-TPP 1 (molecular weight 1 about 1260)

1 P41/300-TPP 1 (molecular weight 1 about 5260) 1 m₁ + m₂ + m₃ + m₄ = 1(100 to 114)

1 P41/300-TPP_(2 1 (molecular weight 1 about 5520) 1 m) ₁ + m₂ + m₃ + m₄= 1 (100 to 114)

EXAMPLE 8 Hydroformylation of 1-dodecene Using Rh/M41/40-TPP as Catalyst

26.6 ml of 1-dodecene (120 mmol) are metered into the abovementionedsteel autoclave containing the catalyst solution using a pump under theexisting pressure of 25 bar. The synthesis gas pressure is thenincreased to 50 bar and kept constant within a pressure band of 5 bar.The reaction temperature is 125° C. After a reaction time of 90 min, nomore gas is absorbed and the reaction is stopped by switching off thestirrer. The autoclave is cooled to 25° C. and, after a settling time of60 min, the upper product phase is separated from the catalyst phase byphase separation. The degree of conversion of the product phase isanalyzed by gas chromatography (GC) and ¹H-NMR spectroscopy.

The conversion according to GC is 93.4%. The n-tridecanol:2-methyldodecanal ratio is 72:28.

EXAMPLES 9 TO 21 Hydroformylation of 1 -dodecene with Various CatalystsComprising Rhodium and Compounds of the Formula (I)

The examples below are carried out as in Example 8 and with slightchanges to the experimental parameters and also using various compoundsof the formula (I). The catalyst is prepared in an analogous manner, theinitial weights of ligand given in Table I being used. The otherexperimental parameters and the experimental results obtained are givenin Table I.

TABLE I Hydroformylation of 1-dodecene using catalysts comprisingrhodium and compounds of the formula (I) Ex. Ligand Initial weight ofCat. phase p t Yield of aldehyde n:iso ratio Rh loss No. short formligand (g) solvent [ml] [bar] [min] [%] GC (GC) org. phase [ppm]  8M41/40-TPP 2.91 30 ml H₂O 50 90 93.4 72:28 0.22  9 M41/40-TPP 2.91 30 mlPEG 400 50 15 95.8 61:39 0.06 10 M41/40-TPP 2.91 30 ml H₂O 15 60 88.077:23 0.25 11 M350-TPP 1.17 30 ml H₂O 50 15 89.1 72:28 1.9  12 M350-TPP1.17 30 ml H₂O 15 30 82.4 76:24 0.65 13 M500-TPP 1.75 30 ml H₂O 50 3093.0 76:24 0.34 14 M500-TPP 1.75 30 ml H₂O 15 60 85.4 75:25 0.21 15M750-TPP 2.32 30 ml H₂O 50 45 95.0 75:25 0.34 16 M750-TPP 2.32 30 ml H₂O15 180  10.1 79:21 <0.05  17 PEG200-TPP 1.06 30 ml H₂O 50 15 90.0 73:27n.d.* 18 PEG600-TPP 1.99 30 ml H₂O 50 145  89.7 76:24 n.d.* 19PEG1000-TPP 2.91 30 ml H₂O 50 180  50.4 84:16 n.d.* 20 PEG1500-TPP 4.0630 ml H₂O 50 180  46.3 84:16 n.d.* 21 PEG 41/300-TPP 12.1  30 ml H₂O 50180  92.5 75:25 n.d.* Constant conditions: Catalyst preparation from 6mg of rhodium(III) acetate (0.023 mmol), quantity and type of ligands ofthe formula (I) and solvents as given, Rh:ligand of the formula (I)ratio 1:100, Rh:olefin ratio 1:5280, preconditioning conditions: 3 hoursat a synthesis gas pressure of 25 bar Hydroformylation conditions: T =125° C., reaction pressure as given, reaction time as given (until nomore gas is absorbed); phase separation at room temperature, *n.d. = notdetermined

What is claimed is:
 1. A catalyst comprising rhodium and a compound ofthe formula (I)

in which m is a number from 1 to 1000; x is a number from 0 to 4; W is agroup of the formulae —CH₂—CH₂—, —CH(CH3)CH2— or —CH₂CH(CH₃)—; R ishydrogen, a straight-chain or branched C₁-C₅-alkyl radical; or a groupof the formulae

where a, b, c, d and e independently of one another are a number from 0to 1000, at least one of the numbers a, b, c, d and e being greater than0; R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are hydrogen,C₁-C₅-alkyl or a group of the formula

R¹ and R² are identical or different and are a straight-chain, branchedor cyclic C₁-C₃₀-alkyl radical or C₆-C₁₀-aryl radical, which isunsubstituted or substituted by from one to five C₁-C₃-alkyl radicals,or R¹ and R² together with the trivalent P atom form a dibenzophospholylof the formula

 or a 3,4-dimethylphospholyl of the formula

 and L is C₁-C₅-alkyl, C₁-C₅-alkoxy, NO₂, NR³R⁴, where R³ and R⁴independently of one another are hydrogen or C₁-C₄-alkyl, or L is Cl orOH.
 2. The catalyst as claimed in claim 1, wherein R¹ and R² areidentical and are each a straight-chain or branched C₁-C₆-alkyl radical,a cyclohexyl radical or a phenyl radical.
 3. The catalyst as claimed inclaim 1, wherein R is hydrogen, methyl, ethyl, n-propyl, n-butyl or agroup of the formula

in which c¹, d¹ and e¹ independently of one another are a number from 1to 500, and R⁷⁰, R⁸⁰ and R⁹⁰ are identical or different and arehydrogen, methyl, ethyl, n-propyl or n-butyl.
 4. The catalyst as claimedin claim 1, wherein L is methoxy, ethoxy, methyl, ethyl or OH.
 5. Thecatalyst as claimed in claim 1, wherein x is
 0. 6. The catalyst asclaimed in claim 1, which comprises rhodium and the compound of theformula (I) in the molar ratio from 1:1 to 1:200.
 7. The catalyst asclaimed in claim 1 where c¹, d¹, and e¹ independently a number from 2 to300.
 8. A process for the preparation of a catalyst as claimed in claim1, which comprises bringing together a rhodium salt or a rhodium complexand a compound of the formula (I).
 9. The process as claimed in claim 8,wherein the rhodium salt or the rhodium complex and the compound of theformula (I) are dissolved in water.
 10. A process for the preparation ofaldehydes, comprising reacting an olefinic compound having from 3 to 20carbon atoms with carbon monoxide and hydrogen in the presence of acatalyst of the formula (I) as claimed in claim 1 at a pressure from 10to 500 bar and a temperature of from 40 to 200° C. in a reaction mediumwhich comprises an aqueous and an organic phase.
 11. The processaccording to claim 10, wherein the olefinic compound is an α-olefiniccompound.
 12. The process as claimed in claim 10, wherein the catalystis present in an amount corresponding to from 10⁻⁵ to 2×10⁻³ mol ofrhodium per mole of olefinic compound.
 13. The process as claimed inclaim 10, wherein the reaction with carbon monoxide and hydrogen iscarried out at a pressure of from 30 to 80 bar.
 14. The process asclaimed in claim 9, wherein the reaction is carried out at a temperatureof from 80 to 150° C.